Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.     

Effect of V5+ in the complex Li3xLa2/3−xTiO3-LaPO4 system

Lithium fast ion conductors of the composition Li_0.3La_2/3Ti_0.7P_0.3−xV_xO_3.3 (LTV) based on mixtures of Li_3xLa_2/3−xTiO₃ and LaPO₄ were prepared by solid state reaction at high temperature (≈ 1300 °C). AC impedance measurements indicate total conductivities of about 1 × 10⁻⁴ Scm⁻¹ for compositions of x=0∼0.3 at room temperature with an activation energy of ≈18 kJ·mol⁻¹ in the temperature range from 30 to 400 °C. X-ray powder diffraction patterns showed that the LTV system is composed of Li_3xLa_2/3−xTiO₃ perovskite solid solution and LaP_1−xV_xO₄ solid solution.     

High-temperature electrical transport in Al-doped calcium and strontium titanates

The electrical conductivity of perovskite-related oxides CaTi_1−xAl_xO_3−δ and SrTi_1−xAl_xO_3−δ (x=0−0.4) were investigated within the temperature range 900 to 1000 °C and the oxygen partial pressure range between 10⁻²⁰ and 0.21 atm using a dc four-point technique. The materials investigated show predominantly p-type electronic conductivity at high, n-type electronic conductivity at low, and ionic conductivity at intermediate oxygen partial pressures. The values of ionic conductivity in CaTi_1−xAl_xO_3−δ were found to be lower than those in CaTi_1−xFe_xO_3−δ. The effect of aluminium concentration on the high-temperature transport properties was examined. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Effect of mixed glass formers on the crystallization kinetics in AgI–Ag<Subscript>2</Subscript>O–V<Subscript>2</Subscript>O<Subscript>5</Subscript>–MoO<Subscript>3</Subscript> glassy superionic system

The crystallization and glass transition kinetics using differential scanning calorimetry (DSC) in 50AgI–33.33Ag₂O–16.67[(V₂O₅)_1−x –(MoO₃) _x ] superionic glassy system is discussed. Thermal stability of glass, studied using various criteria, does not vary significantly with glass former variation. However, the activation energies for structural relaxation (E _s) at glass transition temperature and crystallization (E _c) obtained using Moynihan and Kissinger, Matusita-Sakka formulations found to exhibit interesting trends with MoO₃ substitution in the glass matrix. It is noticed that the electrical conductivity (σ)–temperature (T) cycles obtained at a typical heating rate of 1 °C/min do exhibit significant thermal events. The conductivity after first heating cycle at room temperature is found to be increasing with MoO₃ content and maximum for x = 0.3 (~10⁻³ Ω⁻¹ cm⁻¹ at 30 °C) which is comparable to that of the host 50AgI–33.33Ag₂O–16.67V₂O₅ glassy system. The parameters obtained from σ–T plots and DSC scans do complement each other in a particular range of composition.     

Hydrothermally prepared oxide-ion and Mixed Conductors based on CeO2

The structure, thermal expansion coefficients, electrical and electrochemical properties of Ce_1−xM_xO_2−δ (M=Bi, La, Pr, Eu, Tb; x=0–0.30) solid solutions, prepared hydrothermally for the first time, are surveyed. For all cation substitution a solubility limit depending on the cation size was found. The uniformly small particle size (10–50 nm) of the hydrothermally prepared materials allows sintering of the samples into highly dense ceramic pellets at 1300–1400 °C, a significantly lower temperature, compared to that at 1600–1650 °C required for samples prepared by solid state techniques. X-ray absorption near edge spectroscopy (XANES) was used for the identification of Tb³⁺/Tb⁴⁺ or Pr³⁺/Pr⁴⁺ ions. The maximum of total conductivity in all solid solutions was found for x ∼ 0.15–0.25 with electronic contribution to the total conductivity ∼ 50 % for Tb/Pr substitution and close to zero in all other cases. The conductivity becomes more ionic with decreasing Tb/Pr substitution. The thermal expansion coefficients, determined from high-temperature X-ray diffraction data, are 11.7×10⁻⁶ K⁻¹ for CeO₂ and slowly decrease for Tb and increase for all other cases with increasing substitution. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Ion-electron transfer in solid solutions Rb2 ? 2xFe2 ? xPxO4

The rubidium monoferrite RbFeO₂-based solid solutions with the composition Rb_{2 − 2x} Fe_{2 − x} P _x O₄ have been synthesized, and their crystal structure and the temperature and concentration dependences of the total and electron conductivities have been studied. The introduction of P⁵⁺ ions has been found to sharply decrease the electron conductivity that prevails in pure rubidium monoferrite and, at the same time, to increase the ionic conductivity. The latter becomes dominant as the phosphorus concentration increases. The maximum rubidium-cation conductivity of the materials under study is ∼3 × 10⁻² S/cm at 300°C and ∼3 × 10⁻¹ S/cm at 700°C. The results have been compared with the previously obtained data for similar solid solutions based on rubidium monogallate and monoaluminate.     

Effect of Sn-doping at Mo-site on the conductivity of La2Mo2O9 series of compounds

Taking oxygen ion conductor La₂Mo₂O₉, as a base compound, a series of Sn-doped La₂Mo_2−x Sn _x O_9−δ, x = 0, 0.01, 0.02, 0.03, 0.05, 0.1, 0.15, 0.2 specimens were prepared and characterized by XRD for phase and crystal structure determination and ac impedance spectroscopy for ac and dc conductivity measurement. We have found that there is slight improvement in overall conductivity of the specimen with x = 0.03 at 800°C compared to the undoped compound at the same temperature. The value of conductivity when extrapolated to 800°C is found to be 0.055 S cm-1 for the specimen with x = 0.03, whereas conductivity of undoped specimen at the same temperature is found to be 0.033 Scm⁻¹.     

Influence of acceptor doping on ionic conductivity in alkali earth titanate perovskites

The electrical conductivity of the SrTi_1−xFe_xO_3−δ, BaTi_1−xFe_xO_3−δ and SrTi_1−xMn_xO_3−δ systems has been studied in a range of oxygen partial pressures between 10⁻¹⁶ and 0.21 atm at 900 and 1000 °C. The materials exhibit predominantly ionic conductivity in a wide range of intermediate oxygen partial pressures. It has been found that in Fe doped strontium and barium titanates, the dependencies of the ionic conductivity on the acceptor concentration show a local maximum near x=0.2. Taking into account that in the CaTi_1−xFe_xO_3−δ system (x=0−0.5), the concentration dependence of the ionic conductivity also has a maximum near x=0.2, it can be concluded that this is a common phenomenon for Fe doped alkali earth titanates. An assumption has been made that a scheme of defect formation devised earlier for Fe doped calcium titanate is applicable for other alkali earth titanates.     

Thermal stability and impedance spectroscopy studies of (Cu, Ni) substituted Bi4V2O11 ceramics

Polycrystalline samples of the oxygen ion conductor Bi₂V_0.9Cu_0.1−xNi_xO_5.35 with various contents of nickel (0 ≤ × ≤ 0.1) were investigated. The X-ray powder diffraction revealed the tetragonal structure of all compositions. DTA curves exhibit effects due to phase transition, one endothermic effect during heating and one exothermic one during cooling. The impedance of the ceramics with Pt electrodes was measured in the frequency range 10⁻¹–10⁷ Hz at constant temperatures between 350 and 920 K. The conductivity was determined by nonlinear least-squares analysis of the impedance spectra. Separation of the total resistance into grain interior and grain boundary components was feasible at temperatures below 580 K. The transition temperatures observed in DTA coincide with those observed in conductivity measurements. A phase transition, involving a reordering process of the oxygen ions is considered to be responsible for this phenomenon. The frequency dependent part of the intragrain conductivity was modeled by a constant phase admittance. The effective hopping rate was estimated by comparing the frequency dependent part and the dc limit of the intragrain conductivity. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997.     

Trap characterization for Bi4Ti3O12 thin films by thermally stimulated currents

Thermally stimulated current (TSC) measurements performed in the 100 K–400 K temperature range on Bi₄Ti₃O₁₂ (BiT) thin films annealed at 550 °C and 700 °C had revealed two trapping levels having activation energies of 0.55 eV and 0.6 eV. The total trap concentration was estimated at 10¹⁵ cm⁻³ for the samples annealed at 550 °C and 3×10¹⁵ cm⁻³ for a 700 °C annealing and the trap capture cross-section was estimated about 10⁻¹⁸ cm². From the temperature dependence of the dark current in the temperature range 20 °C–120 °C the conduction mechanism activation energy was found to be about 0.956–0.978 eV. The electrical conductivity depends not only on the sample annealing temperature but also whether the measurement is performed in vacuum or air. The results on the dark conductivity are discussed considering the influence of oxygen atoms and oxygen vacancies. Received: 28 January 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Synthesis and characterization of Bi-doped zirconia for solid electrolyte

(100-x)ZrO₂(x)Bi₂O₃ (x = 5, 10, 15) system has been synthesized by solid-state reaction technique. Tetragonal Bi_7.38Zr_0.62O_12.31 phase has formed in all the samples after sintering at 850 °C for 24 h. Apart from this, ZrO₂ and Bi₂O₃ are also identified as minority phases. The volume fraction of Bi_7.38Zr_0.62O_12.31 phase increases with increasing concentration of Bi₂O₃. The AC conductivity plots exhibit phase transition at 570 °C and 460 °C for x = 10 and x = 15 samples, respectively. The maximum conductivity is observed (1.60 mS/cm) in x = 15 sample. These results are correlated and supported with microstructural and thermal analysis.     

Structural studies and ionic conductivity of CuCr1−xVxS2 (0 ≤ × ≤ 0.3)

CuCr_1−xV_xS₂ (0 ≤ × ≤ 0.3) is isostructural with CuCrS₂. The substitution of Cr by V results in the partial transition of Cu atoms into the disordered state and in an increasing Cu⁺ ion conductivity.     

Thermostimulated surface autosegregation in bismuth ferrite single crystals

The chemical and phase composition and morphological features of the surface nanostructure have been studied by the methods of high-resolution scanning electron microscopy, X-ray microprobe analysis, and atomic force microscopy in bismuth ferrite single crystals. This structure was formed as a result of the thermostimulated surface segregation after annealing in air or vacuum at the pressure of 10⁻⁴ Pa. It has been experimentally found that, at temperatures less than 500°C, Bi₂F₄O₉ nanoparticles were formed due to the selective diffusion of iron atoms to the surface. Starting from 300°C in vacuum and 450°C in air, the segregating atom type changed and nanophases with high bismuth concentration (sillenites Bi_{26 − x} Fe _x O₃₉ and Bi₂O₃ appeared in some regions. The partial orientation of new phases has been observed in some surface regions. A probable mechanism of the described phenomenon that represents a combination of selective intrinsic mass-transport of atoms from the bulk to the surface and their thermal evaporation has been discussed.     

The effect of LaPO4 in the LixLa2/3Ti1−xPxO3+x system

Lithium ion conductors of the overall composition Li_xLa_2/3Ti_1−xP_xO_3+x (hereafter referred to as LTP) based on La_2/3TiO₃ were prepared by solid state reaction at high temperature (1300 °C). AC impedance measurements indicate that the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ when x=0.28 − 0.35 at room temperature and have an activation energy of 18 kJ·mol⁻¹ in the temperature range from room temperature to 400 °C. X-ray powder diffraction patterns showed that the LTP system has a complex composition, which contains the solid solution perovskite Li_3xLa_2/3−xTiO₃ and LaPO₄.     

Preparation,proton transport properties and use in gas sensors of thin films of zirconium phosphate with γ-layered structure

Pellicular γ-zirconium phosphate (γ-ZP_(p)), i.e. sheets made up entirely of oriented lamellae of Zr(PO₄)(H₂PO₄)·2H₂O (γ-ZP), have been obtained by filtering colloidal dispersions of exfoliated γ-ZP in water/acetone. The ac-conductivity of γ-ZP_(p) and γ-ZP was measured in the temperature range 20/–20°C on samples previously conditioned at relative humidities between 90 and 5%. In both cases, the conductivity dependence on material hydration indicates the presence of a non-negligible bulk transport at low relative humidities. For each relative humidity the conductivity data have been parameterised on the basis of the Arrhenius equation. Activation energy and pre-exponential factor values suggest the presence of the same conduction mechanism in both materials. The conductivity of γ-ZP_(p) measured by applying the electric field parallel to the sheets ranges from 3·10⁻⁴ to 1·10⁻⁵ S cm⁻¹ for relative humidity decreasing from 90 to 11%, being an order of magnitude higher than that of γ-ZP. Since the pellicular and microcrystalline material have very similar surface areas (11–12 m²/g), the higher conductivity of γ-ZP_(p) is mainly due to the preferred particle orientation parallel to the electric field. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Electrical conductivity and chemical stability of perovskite-type BaCe0.8-xTixY0.2O3-δ

Here we report the synthesis, chemical stability, and electrical conductivity of Ti-doped perovskite-type BaCe_0.8-x Ti _x Y_0.2O_3-δ (x = 0.05, 0.1, 0.2, and 0.3; BCTY). Samples were synthesized by conventional solid state (ceramic) reaction from corresponding metal salts and oxides at elevated temperature of 1,300–1,500 °C in air. The powder X-ray diffraction confirmed the formation of a simple cubic perovskite-type structure with a lattice constant of a = 4.374(1), 4.377(1), and 4.332(1) ? for x = 0.05, 0.1, and 0.2 members of BCTY, respectively. Like BaCe_0.8Y_0.2O_3-δ (BCY), Ti substituted BCTY was found to be chemically not stable in 100% CO₂ and form BaCO₃ at elevated temperature. The bulk electrical conductivity of BCTY decreased with increasing Ti content and the x = 0.05 member exhibited the highest conductivity of 2.3 × 10⁻³ S cm⁻¹ at 650 °C in air, while a slight increase in the conductivity, especially at low temperatures (below 600 °C), was observed in humidified atmospheres.     

Effects of La–Zn substitution on microstructure and magnetic properties of strontium ferrite nanofibers

Sr_1−x La _x Zn _x Fe_12−x O₁₉/poly(vinylpyrrolidone) (PVP) (0.0≤x≤0.5) precursor nanofibers were prepared by the sol–gel assisted electrospinning method from starting reagents of metal salts and PVP. Subsequently, the Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers with diameters of around 100 nm were obtained by calcination of the precursor at 800 to 1000°C for 2 h. The precursor and resultant Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer and vibrating sample magnetometer. The grain sizes of Sr_0.8La_0.2Zn_0.2Fe_11.8O₁₉ nanofibers are in a nanoscale from 40 to 48 nm corresponding to the calcination temperature from 800 to 1000°C. With La–Zn substitution content increase from 0 to 0.5, the grain size and lattice constants for the Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers obtained at 900°C show a steady reduction trend. With variations of the ferrite particle size arising from the La–Zn substitution, the nanofiber morphology changes from the necklace-like structure linking by single elongated plate-like particles to the structure building of multi-particles on the nanofiber cross-section. The specific saturation magnetization of Sr_1−x La _x Zn _x Fe_12−x O₁₉ nanofibers initially increases with the La–Zn content, reaching a maximum value 72 A m² kg⁻¹ at x=0.2, and then decreases with a further La–Zn content increase up to x=0.5, while the coercivity exhibits a continuous reduction from 413 (x=0) to 219 kA m⁻¹ (x=0.5). The mechanism for the La–Zn substitution and the nanofiber magnetic property are analyzed.     

CO(III)–NI(II) double substituted bismuth vanadate: synthesis,phase stabilization,and structural and electrical characterization

Samples of Co–Ni double substituted bismuth vanadate, BICO_0.20?x NI _x VOX (Bi₄Co_0.20???x ^(III)Ni _x ^(II)V_1.8O_{10.8???(x/2)???δ} ;0?≤?x?≤?0.20) were synthesized by standard solid state reactions. The influence of Ni substitution for Co on phase stabilization and oxide-ion performance have been investigated using X-ray powder diffraction, differential thermal analysis, and AC impedance spectroscopy. The high conducting γ′-phase was effectively stabilized at room temperature for compositions with x?≥?0.13 whose thermal stability increases with Ni content. The complex plane plots of impedance were typically represented at temperatures below 380 °C, suggesting a major contribution of polycrystalline grains to the overall electrical conductivity. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. Interestingly, the maximum ionic conductivity at lower temperatures (～2.56?×?10^?4 S cm^?1 at 300 °C) was observed for the composition with x?=?0.13. However, a good agreement was generally found between the values of electrical conductivity and corresponding activation energies of conduction.     

Defects and transport in SrFe1−xCoxO3−δ

The non-stoichiometry and chemical diffusion coefficient of SrFe_1−xCo_xO_3-δ have been measured by steady state and transient thermogravimetry in the temperature range 750–1200 °C at different oxygen partial pressures. At high oxygen partial pressures, the chemical diffusion coefficient was in the range 1·10⁻⁴ – 7·10⁻⁴ cm²/s. This, combined with high concentration of disordered vacancies make these materials perhaps the fastest solid oxygen ion diffusers known at high temperatures and high oxygen partial pressures. However, due to the high concentration of defects in SrFe_1−xCo_xO_3-δ the compound transforms from a cubic (disordered) perovskite to a brownmillerite type of structure under reduced oxygen partial pressures below approx. 900 °C. Due to this phase transition, the mobility of oxygen vacancies in SrFe_1−xCo_xO_3-δ decreases up to about an order of magnitude at 850 °C. We also observe an ordering effect at 1000 °C, although smaller in size, and this is suggested to be due to short range ordering of four-coordinated polyhedra of Fe. For possible use as oxygen separation membranes, phase stability against sulphur and carbon containing atmospheres is also discussed with respect to the formation of carbonates and sulphates. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Power factor of very thin thermoelectric layers of different thickness prepared by laser ablation

Room temperature conductivity and the Seebeck coefficient of thin layers prepared by laser ablation from Bi₂Te₃ target were explored. The power factor was calculated for samples prepared at substrate temperature of 360°C with the density of the laser beam 5 J cm⁻² and at substrate temperature of 410°C with the density of the laser beam 2 J cm⁻² during the deposition. Oscillations of the conductivity and the power factor with the layer thickness were observed at room temperature. The oscillations of conductivity were also verified at the temperature of 77 K. The period of oscillations depends on the preparation conditions. This behavior has been theoretically explained by the quantum size effect in the layers containing different phases and in addition, it was demonstrated by the X-ray Diffraction measurement. The behavior of the power factor of the layers is compared to the behavior of the figure of merit of the layers published earlier.